Analytical Characterization Methods for Crude Oil and Related Products

Description

Basic theory, applications, and recent trends in analytical techniques used in crude oil and related products analysis

This book covers the application of different spectroscopic methods to characterize crude oil and related products. Its topics are presented in a pedagogical manner so that those new to the subject can better understand the content. The book begins by familiarizing the reader with the rheological characterization of crude oil and related products. Subsequent chapters are directed towards the current trends of different spectroscopic methods for the characterization of crude oil.

Analytical Characterization Methods for Crude Oil and Related Products features chapters on: optical interrogation of petroleum asphaltenes (myths and reality); ESR characterization of organic free radicals in petroleum products; high-field, pulsed, and double resonance studies of crude oils and their derivatives; NMR spectroscopy in bitumen characterization; applications of Raman spectroscopy in crude oil and bitumen characterization; and more.

Uses a bottom-up approach—starting from the basic theory of the technique followed by its applications and recent trends in crude oil analysis
Includes informative content so as to take a technician to the level of using a particular analytical method
Covers relevany information so as to enable a manager in the industry to make purchasing decisions

Analytical Characterization Methods for Crude Oil and Related Products is aimed at researchers in academia as well as technicians and developers of new analytical methods in the oil industry and related areas. It will also be of interest to professionals, scientists, and graduate students in analytical sciences dealing with oil and environmental analysis.

Cover 2
Title Page 6
Copyright 7
Dedication 8
Contents 10
List of Contributors 16
Preface 20
Chapter 1 Rheological Characterization of Crude Oil and Related Products 22
- 1.1 Introduction 22
- 1.2 Sample Preparation for Rheological Characterization 23
  - 1.2.1 Ensuring the Chemical Stability 23
  - 1.2.2 Choosing the Rheometer Geometry 24
  - 1.2.3 Erasing the Thermal Memory 25
  - 1.2.4 Performing the Cooling Process 25
- 1.3 Rheological Tests 26

Cover 2
Title Page 6
Copyright 7
Dedication 8
Contents 10
List of Contributors 16
Preface 20
Chapter 1 Rheological Characterization of Crude Oil and Related Products 22
- 1.1 Introduction 22
- 1.2 Sample Preparation for Rheological Characterization 23
  - 1.2.1 Ensuring the Chemical Stability 23
  - 1.2.2 Choosing the Rheometer Geometry 24
  - 1.2.3 Erasing the Thermal Memory 25
  - 1.2.4 Performing the Cooling Process 25
- 1.3 Rheological Tests 26
- 1.4 Potential Sources of Errors 30
- References 31
Chapter 2 Optical Interrogation of Petroleum Asphaltenes: Myths and Reality 34
- 2.1 Introduction 34
  - 2.1.1 What are Asphaltenes? 34
  - 2.1.2 The Reasons for Intensive Asphaltene Research 35
  - 2.1.3 No Controversy about the Elemental Composition of Asphaltenes 36
  - 2.1.4 Continuing Debates on the Size and the Structure of Asphaltene Molecules and Aggregates 36
  - 2.1.5 Conflicting Paradigms based on Similar Analytical Techniques: Apparent Significance of "Human Factors" 39
- 2.2 Mythical "Characteristic Signatures" of Asphaltenes in Optical Analytical Methods 40
  - 2.2.1 Nonexistent "Resonance UV Absorption" of Asphaltenes 40
  - 2.2.2 Mythical "Characteristic Monomer Peaks" in Fluorescence Emission Studies 44
- 2.3 Misconceptions about the Properties of UV/Vis Absorption Spectra of Asphaltenes 50
  - 2.3.1 The Myth about the Absence of Asphaltene Aggregation Effects in Optical Absorption Studies 51
  - 2.3.2 The Myth about the "Urbach Tail" in Optical Absorption Spectra of Asphaltenes and Crude Oils 55
    - 2.3.2.2 Urbach Range 56
    - 2.3.2.3 Low Absorption (Defects) Range 56
    - 2.3.2.1 Tauc Range 56
  - 2.3.3 In the UV/Vis Spectral Range Asphaltenes Apparently Act not as Absorbers, but as Scatterers 59
- 2.4 Current State of Knowledge about Asphaltene Monomers and Primary Asphaltene Aggregates 63
  - 2.4.1 Some Requirements for Preparation of Dilute Asphaltene Solutions 65
  - 2.4.2 Multiple States/Phases of Primary Asphaltene Aggregates Revealed by Optical Absorption Measurements 67
  - 2.4.3 Multiple States/Phases of Primary Asphaltene Aggregates Revealed by Refractive Index Measurements 68
    - 2.4.3.2 Standard Deviation of Refractive Index at Concentrations below CNAC 71
    - 2.4.3.1 Mean Refractive Index at Concentrations below CNAC 71
  - 2.4.4 Conditions for Observation of Asphaltene Monomers and Evolution of Primary Asphaltene Aggregates Revealed by Fluorescence 74
    - 2.4.4.1 Studies of Steady-State Fluorescence Emission 74
    - 2.4.4.2 Studies of Time-Resolved Fluorescence Emission 76
  - 2.4.5 Evolution of Primary Asphaltene Aggregates Revealed by Mass Spectrometry 77
  - 2.4.6 "Optical Interrogation" Reveals that Primary Asphaltene Aggregates are Porous and Entrap/Occlude Molecules of Metalloporph 79
  - 2.4.7 Apparent Absence of "Consecutive Aggregation" in Asphaltene Experiments: Revised Description of the Observed Non-monotonic 83
- References 86
Chapter 3 ESR Characterization of Organic Free Radicals in Crude Oil and By-Products 98
- 3.2 Organic-Free Radicals in Crude Oil 98
- 3.1 Introduction 98
- 3.3 ESR of Crude Oil 99
- 3.4 By-Product Oil by ESR 106
- 3.5 ESR and Calculations on the Electronic Structure of Free Radicals in Oil By-Products 114
- References 117
Chapter 4 High-Field, Pulsed, and Double Resonance Studies of Crude Oils and their Derivatives 122
- 4.1 Introduction 122
- 4.2 EPR: Basic Principles and Magnetic Interactions 124
- 4.3 EPR Pulse Sequences 130
- 4.4 Application Examples 133
  - 4.4.1 W-Band, Relaxation Studies of VO2+ and FR in Asphaltenes Fractions 133
  - 4.4.2 ENDOR of VO2+ in Crude Oil Samples 137
- References 142
- 4.5 Conclusion 142
- Acknowledgments 142
Chapter 5 NMR Spectroscopic Analysis in Characterization of Crude Oil and Related Products 146
- 5.1 Introduction 146
- 5.2 1H NMR and 13C NMR Spectroscopy Analysis Methods 147
- 5.3 NMR Techniques 148
- 5.4 Application of NMR Analysis in Characterization of Crude Oil and Related Products 150
- 5.5 Asphaltene Characterization using NMR Techniques 155
- References 158
- 5.6 Conclusions 158
Chapter 6 NMR Spectroscopy in Bitumen Characterization 162
- 6.1 Introduction 162
- 6.2 1H and 13C NMR Spectroscopy 164
- 6.3 Phosphorus-31 NMR Spectroscopy 173
- 6.4 NMR Imaging and Solid-State NMR 175
  - 6.4.1 Solid-State NMR 175
  - 6.4.2 NMR Imaging 176
- 6.5 Conclusion 177
- References 178
Chapter 7 Applications of Low Field Magnetic Resonance in Viscous Crude Oil/Water Property Determination 184
- 7.1 Introduction 184
- 7.2 Background for NMR Measurements 186
  - 7.2.1 Interpretation of NMR Relaxation Rates 188
  - 7.2.2 Interpretation of NMR Amplitudes 192
- 7.3 Fluid Content in Oil/Water Systems 196
- 7.4 Oil Viscosity from NMR 202
  - 7.4.1 Viscosity Predictions in High Viscosity Bitumen 208
  - 7.4.2 Viscosity Predictions in Oilfield Emulsions 210
- 7.5 Fluid Saturations and Viscosity in Porous Media 213
  - 7.5.1 Prediction of Saturations and Viscosity from T2 relaxation distributions 214
  - 7.5.2 Prediction of Saturations from T1-T2 Relaxation Distributions 221
- 7.6 NMR in Oil-Solvent Systems 227
  - 7.6.1 Predictions of Solvent Content in Oil-Liquid Solvent Systems 228
  - 7.6.2 Predictions of Non-Equilibrium Viscosity in Oil-Vapor Solvent Systems 234
- 7.7 Summary of NMR and Fluid Property Measurements 236
- Acknowledgments 237
- References 238
Chapter 8 Application of Near-Infrared Spectroscopy to the Characterization of Petroleum 242
- 8.1 Introduction 242
- 8.2 Sample Handling and Preparation 243
- 8.3 Near-Infrared Spectroscopy 244
  - 8.3.1 Near-Infrared in Refineries 248
- 8.4 Chemometrics 249
  - 8.4.1 Pretreatment 249
    - 8.4.1.1 Smoothing 249
    - 8.4.1.2 Multiplicative Scatter Correction 249
    - 8.4.1.3 Mean Centering 250
    - 8.4.1.4 Derivation 251
  - 8.4.2 Calibration Model 251
    - 8.4.2.1 Principal Component Analysis (PCA) 252
    - 8.4.2.2 Partial Least Squares Regression 253
    - 8.4.2.3 Artificial Neural Networks 255
  - 8.4.3 Validation 255
  - 8.4.4 Other Methods 256
- 8.5 Commercial NIR Equipment and Industrial Applications 257
  - 8.5.1 Industrial Applications 257
    - 8.5.1.4 Ethanol Fermentation 259
    - 8.5.1.2 Crude Distillation Optimization 259
    - 8.5.1.5 Conjugated Diolefins in Pygas 259
    - 8.5.1.3 Product Blending 259
    - 8.5.1.6 Regulatory Fuel Screening 259
    - 8.5.1.1 Pipeline Product Analysis and Identification 259
  - 8.6 Conclusions 260
  - References 260
- Chapter 9 Raman and Infrared Spectroscopy of Crude Oil and its Constituents 266
  - 9.1 Introduction 266
  - 9.2 Fundamentals of Raman and Infrared Spectroscopy 267
  - 9.3 Infrared Spectroscopy 270
  - 9.4 Raman Spectroscopy 272
  - 9.5 Evaluation of Vibrational Spectra 278
  - 9.6 Applications 282
  - 9.7 Conclusion 287
  - References 288
- Index 292
- EULA 299

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